The present invention generally relates to ink-jet printing, and in particular, to a specific ink set suitable for use with an off-axis printer system.
Ink-jet printing is a non-impact printing process in which droplets of ink are deposited on a print medium in a particular order to form alphanumeric characters, area-fills, and other patterns thereon. Low cost and high quality of the hardcopy output, combined with relatively noise-free operation, have made ink-jet printers a popular alternative to other types of printers used with computers. One particular type of ink-jet printer, known as an off-axis printer, includes a replaceable print cartridge A fluid interconnect on the print cartridge connects it to a separate ink supply located within the printer.
The non-impact printing process of ink-jet printing involves the ejection of fine droplets of ink onto a print medium such as paper, transparency film, or textiles in response to electrical signals generated by a microprocessor. There are two basic means currently available for achieving ink droplet ejection in ink-jet printing: thermally and piezoelectrically. In thermal ink-jet printing, the energy for drop ejection is generated by electrically heated resistor elements, which heat up rapidly in response to electrical signals from a microprocessor to create a vapor bubble, resulting in the expulsion of ink through nozzles associated with the resistor elements. In piezoelectric ink-jet printing, the ink droplets are ejected due to the vibrations of piezoelectric crystals, again, in response to electrical signals generated by the microprocessor.
Commercially-available off-axis ink-jet printers, such as a DeskJet(copyright) 2200 printer available from Hewlett-Packard Company, use inks of differing hues, namely, magenta, yellow, and cyan, and optionally black. The particular set of colorants, for example, dyes, used to make the inks is called a xe2x80x9cprimary dye set.xe2x80x9d A spectrum of colors, e.g., secondary colors, can be generated using different combinations of the primary dye set.
Any given perceived color can be described using any one of the color spaces, as is well known in the art. For example, in the CIELAB color space, a color is defined using three terms L*, a*, and b*. L* defines the lightness of a color, and it ranges from zero (black) to 100 (white). The terms a* and b*, together, define the hue and chroma characteristics of a given color. The term a* ranges from a more negative number, green, to a more positive number, red. The term b* ranges from a more negative number, blue, to a more positive number, yellow.
To determine the concentration or amount of a given substance (e.g., a dye) in a solution, absorbance is commonly used by chemists. Many molecules and ions have the ability to absorb visible light. When these ions or molecules are present in solution, the amount of light absorbed is directly related to the number of molecules in solution. Each ion or molecule will have characteristic absorption spectra wherein the various wavelengths of light present in visible xe2x80x9cwhitexe2x80x9d light are differentially absorbed. It is desirable in most cases to measure the absorbance where the absorbance is strongest (lambdamax) or most sensitive. Absorbance values can be calculated according to Beers Law:
Absorbance=Ebc where
a. E is equal to molar absorptivity which is an intrinsic property of the molecule
b. b is equal to the path length the light must travel
c. c is equal to the solution concentration
The resulting absorbance value can then be applied to determine the concentration of molecules. In the case of dyes, the absorbance is taken as the measure of concentration or amount of dye molecules present, just as weight would be used if dry material were used. In the manufacture of inks using dyes, it is desirable to use absorbance due to the expense associated in drying dyestuffs for the sole purpose of measuring the same by dry weight and redissolving them. There are health hazards associated with handling dried dye that require expensive safety procedures to be implemented and, often times, the raw dye from the manufacturer is not 100% pure, creating further problems. When working with a dyestuff that is not 100% pure, dry weight of dye is actually misleading as a given dry weight of dye could contain a variable number or concentration of dye molecules dependant on the purity, which are the functional element in the ink. By using absorbance as a measure of dye concentration the accurate reproducible manufacture of inks using dyes is assured.
In general, a successful ink set for color ink-jet printing must have the following properties: good crusting resistance, good stability, the proper viscosity, the proper surface tension, good color-to-color bleed alleviation, rapid dry time, consumer-safety, and low strike-through. When placed into a thermal ink-jet system, the ink set must also be kogation-resistant.
In addition, the ink set must be able to provide printed images having good color characteristics, such as correct hue and high chroma. While formation of colors on plain paper is required, it is also necessary that the ink set be useful on other print media, such as transparency film,coated paper, and photo paper. Another requirement for the ink set is to provide a hard copy output that is lightfast, thus preserving the integrity of the original color information.
While some of these conditions may be met by ink vehicle design, other conditions must be met by the proper selection and combination of the colorants. The selection of the colorants becomes especially important when additional limitations are placed on the choice of the colorants because of other system requirements, such as the color-to-color bleed control mechanism.
Regardless of whether an ink is dye-based or pigment-based, ink-jet inks commonly face the challenge of color-to-color or black-to-color bleed control. The term xe2x80x9cbleed,xe2x80x9d as used herein, is defined to be the invasion of one color into another, once the ink is deposited on the print medium, as evidenced by a ragged border of mixed color therebetween. Bleed occurs as colors mix both on the surface of the paper substrate as well as within the substrate itself. The occurrence of bleed is especially problematic between a black ink and an adjacently-printed color ink because it is all the more visible. Hence, to achieve good print quality, bleed must be substantially reduced or eliminated such that borders between colors are clean and free from the invasion of one color into the other.
Many proposals are made to obtain high quality ink compositions for ink-jet printing which attempt to meet the above-mentioned characteristics. Although various inks are known which possess one or more of the of the foregoing properties, few inks possess all of these properties, since an improvement in one property often results in the degradation of another property. For example, to obtain improved color reproduction performance, U.S. Pat. No. 5,143,547 discloses the combination of C.I. Acid Yellow 23, C.I. Direct Red 227, and C.I. Acid Blue 9; while U.S. Pat. No. 5,145,519 discloses the combination of C.I. Direct yellow 86, C.I. Acid Red 52, and C.I. Acid Blue 9. These sets of ink compositions, however, possess a number of shortcomings. For example, the C.I. Yellow 23 for use in the yellow ink composition disclosed in U.S. Pat. No. 5,143,547 has poor light resistance.
A different approach used for controlling bleed between the printed images, as disclosed in U.S. Pat. No. 5,428,383, is to provide a first ink composition comprising a first colorant, and a second ink composition comprising a second colorant and a precipitating agent (e.g., inorganic salts), which will react with the first colorant in the first ink composition so that upon contact of the first ink and the second ink on the printing medium a precipitate is formed, thus preventing color bleed between the first ink composition and the second ink composition.
Likewise, many inks used commercially represent a compromise in an attempt to achieve an ink evidencing at least an adequate response in each of the aforementioned characteristics. For example, a number of inks and ink sets suffer from black to color bleed which make their use less desirable or impossible for a number of color-intensive printing applications. Likewise, many of the known inks and ink sets suffer from poor lightfastness and humid hue shift/bleed on special media. Other problems are encountered when attempting to use these known inks and ink sets in reservoir based off-axis printing systems. In view of the foregoing, there exists a need in the industry for inks that work well in both fiber and foam based off-axis systems as well as in pens/cartridges without any fiber or foam material, and for ink formulations which have improved properties and which do not improve one property at the expense of the others, such as image quality, light fastness, architecture, performance and reliability. More specifically, there exists a need for improved black-to-yellow (K/Y) bleed for faster plain paper printing, no humid hue shift/bleed for magenta inks on special media, good plain paper chroma and lightfastness, and/or compatibility of inks with new reservoir material in an ink supply (e.g., as seen in off-axis system cartridges)
Color ink sets suitable for use in ink-jet printers are provided. In accordance with the invention, a set of color inks for use in printer systems are provided and formulated to provide improved plain paper and special media performance while maintaining good printing characteristics. The inks and ink sets of the present invention exhibit excellent color performance and lightfastness across a range of media, robust K/Y bleed resistance on plain paper at fast print speeds, as well as excellent printability and reliability. Furthermore, the ink set enables good reliability in an environment having a relatively high concentration of precipitating agents. This reliability enables the use of precipitation bleed control mechanisms. The inks and ink sets of the present invention also work equally well in a synthetic fiber or foambased (e.g., polyurethane foam) or a fiberless (foamless) system.
More specifically, a specific dye set for formulating yellow, magenta, and cyan inks is disclosed, a yellow dye comprising a mixture of acid yellow 23 (AY23) and direct yellow 132 (DY132), a cyan dye comprising a mixture of acid blue 9 (AB9) and a cyan dye compound having the formula:
xe2x80x94(SO3H)2.7
CuPcxe2x80x94(SO2NH2)0.5
xe2x80x94(SO2NH(C2H4 OH)0.8
wherein Pc represents a phthalocyanine nucleus (as disclosed in Patent Application No. WO 99/67334, the contents of which are incorporated herein by reference); and a magenta dye comprising a magenta dye compound having formula: 
wherein Q is a cation.
The invention described herein is directed to a specific ink set for printing ink-jet images using commercially available ink-jet printers, such as DESKJET(copyright)(copyright) printers, and more particularly, off-axis ink-jet printers, such as the DESKJET 2200(copyright) printer, manufactured by Hewlett-Packard Company of Palo Alto, Calif. The ink set enables an ink-jet color printer to produce high quality color images having excellent color performance and lightfastness on a range of media, particularly on plain paper. Furthermore, the ink set enables good reliability, such as ink stability, and decap and recovery (e.g. crusting) in a variety of environments.
The present yellow, magenta, and cyan aqueous ink compositions each comprise in general from about 0.05 to about 20 wt % of at least one dye and a vehicle comprising the following components (in wt % of total ink composition): from about 5 to about 30 wt % of at least one organic solvent; 0 to about 5 wt % of at least one component independently selected from the group consisting of surfactants, buffers, precipitating agents and biocides. All concentrations herein are in weight percent of total ink composition, unless otherwise indicated. The purity of all components is that employed in normal commercial practice for ink-jet inks. In the practice of the invention, each ink color, namely, yellow, magenta, and cyan can comprise more than one dye load. That is, there can be one or more ink-jet ink supplies filled for each ink color, each supply having a different dye load or a different dye. As used herein, the term xe2x80x9cinkxe2x80x9d refers to the inks of the present invention.
In selecting the colorants for the ink set of the present invention, the following factors were considered: reduced or absence of humid hue shift; good color performance, particularly, on plain paper; good lightfastness; good black to color bleed resistance; excellent printability and readability; and compatibility of inks with reservoir fiber-based materials in the ink supply. Of particular importance in the present invention was the selection of appropriate colorants capable of providing the aforementioned characteristics in a reservoir-based off-axis printer, as well as providing those attributes in a printer or pen lacking such a fiber material.
In order to achieve the above-mentioned goals, the dyes or colorants selected for the present ink set should exhibit good compatibility (e.g., stable in the ink vehicle) in various environments. For example, the selected colorants should exhibit little, if any, significant reactivity with precipitating agents when these two materials (i.e., colorant and precipitating agent) are formulated in the same ink and should remain soluble when formulated with a precipitating agent. In other words the dyes should have sufficient solubility in the ink vehicle so that they would not form unwanted levels of precipitate by the precipitating agents or through reaction with other components in the ink. Additionally, the dyes should not react with the precipitant to form unwanted levels of compounds that will, either immediately or over time, drop out of solution. For example the dyes should not form insoluble complexes or salts that have a tendency to form aggregates that have decreased solubility in the ink vehicle over time in such levels as to interfere with the desired performance of the printing system.
The selected colorants must also exhibit good lightfastness on a wide range of media, particularly, special paper. It is also important that the colorants produce highly chromatic printed images having the appropriate hue, especially on plain paper.
It was found that many of the dyes that satisfied the first two requirements, namely, good solubility and lightfastness, produced printed images that (1) deviated from the ideal hue angle targets on plain paper, and/or (2) had low chroma on plain paper.
The dye set of the present invention, provides good color gamut on plain paper; good lightfastness; improved K/Y bleed, good pH stability, and good printing performance. The ink set of the present invention comprises:
a yellow ink comprising a mixture of acid yellow 23 (AY23) and direct yellow 132 (DY132);
a cyan ink comprising a mixture of acid blue 9 (AB9) and a cyan dye compound having the formula:
xe2x80x94(SO3H)2.7
CuPcxe2x80x94(SO2NH2)0.5
xe2x80x94(SO2NH(C2H4OH)0.8
xe2x80x83wherein Pc represents a phthalocyanine nucleus; and
a magenta ink comprising a magenta dye having the formula: 
xe2x80x83wherein Q is a cation. In a preferred embodiment, Q is independently selected the group of cations consisting of ammonium, substituted ammonium, sodium, lithium, potassium, and tetramethylammonium ion.
The inks of the present invention comprise from about 0.05 to about 20% dye; preferably, from about 0.1 to about 8%; and more preferably, from about 0.5 to about 5%; by weight, based on the total weight of the ink, based on the sodium form of the dyes. It should be understood that the actual salt form of the dye used in the ink may be different (e.g., the dye may be in the TMA form). The dyes may be in their salt form, such as an alkali metal (Na, K, or Li) or quaternary ammonium. Some of these salt forms, such as Na, are commercially available. Other salt forms can be made using well known techniques.
In one embodiment, the inks of the present invention comprise: at least one yellow ink having a visible light absorbance of from about 0.242 to about 0.620 at a lambdamax of from 404 to 412 and at a 1:5,000 dilution in water; at least one cyan ink having a visible light absorbance of from about 0.08 to about 1.55 at a lambdamax of from 624 to 632 and at a 1:5,000 dilution in water; at least one magenta ink having a visible light absorbance of from about 0.020 to about 0.807 at a lambdamax of from 540 to 550 and at a 1:10,000 dilution in water. In a more preferred embodiment the inks of the present invention comprise: at least one yellow ink having a visible light absorbance of from about 0.299 to about 0.451 at a lambdamax of from 404 to 412 and at a 1:5,000 dilution in water; at least one cyan ink having a visible light absorbance of from about 0.16 to about 0.80 at a lambdamax of from 624 to 632 and at a 1:5,000 dilution in water; at least one magenta ink having a visible light absorbance of from about 0.061 to about 0.404 at a lambdamax of from 540 to 550 and at a 1:10,000 dilution in water. In a most preferred embodiment, the inks of the present invention comprise: at least one yellow ink having a visible light absorbance of from about 0.348 to about 0.404 at a lambdamax of from 404 to 412 and at a 1:5,000 dilution in water; at least one cyan ink having a visible light absorbance of from about 0.335 to about 0.400 at a lambdamax of from 624 to 632 and at a 1:5,000 dilution in water; at least one magenta ink having a visible light absorbance of from about 0.150 to about 0.170 at a lambdamax of from 540 to 550 and at a 1:10,000 dilution in water.
Consistent with the requirements for this invention, various types of additives, as is commonly practiced in the art, may be employed in the inks to optimize the properties of the ink compositions for specific applications.
Precipitating Agent
Precipitating agents may be used to further enhance the characteristics of the ink set of the present invention. The precipitating agent is preferably of a type which upon contact (for example on the print medium) reacts with the anionic group (e.g., the anionic group such as carboxyl or sulfonate) associated with a colorant (such as a dye, or a self-stabilized pigment, or the ionic group on a dispersant associated with a dispersed pigment) in the ink (i.e., second ink) composition to form an insoluble salt, complex, or compound.
Vehicle
The inks of the present invention comprise an aqueous vehicle comprising the following components (in wt % of total ink composition): from about 5 to about 30 wt % of at least one water soluble organic solvent; 0 to about 5 wt % of at least one component independently selected from the group consisting of surfactants, buffers, biocides, and metal chelators; and the balance water.
Organic Solvent
The inks of the present invention comprise from about 5 to about 35 wt % organic solvent. More preferably, the inks comprise from about 10 to about 30 wt % organic solvent, with a concentration from about 15 to about 25 wt % being the most preferred.
The water soluble organic solvents suitably employed in the present ink-jet ink compositions include any of, or a mixture of two or more, of such compounds as nitrogen-containing heterocyclic ketones, such as 2-pyrrolidone, N-methyl-pyrrolid-2-one (NMP), 1,3-dimethylimidazolid-2-one, and octyl-pyrrolidone; diols such as ethanediols, (e.g., 1,2-ethandiol), propanediols (e.g., 1,2-propanediol, 1,3-propanediol, 2-ethyl-2-hydroxy-methyl-1,3-propanediol, ethylhydroxy-propanediol), butanediols (e.g., 1,2-butanediol, 1,3-butanediol, 1,4-butanediol), pentanediols (e.g., 1,2-pentanediol, 1,5-pentanediol), hexanediols (e.g., 1,6-hexanediol, 2,5-hexanediol, 1,2-hexanediol), heptanediols (e.g., 1,2-heptanediol, 1,7-heptanediol), octanediols (e.g., 1,2-octanediol, 1,8-octanediol); glycol ethers and thioglycol ethers, commonly employed in ink-jet inks, such as polyalkylene glycols such as polyethylene glycols (e.g., diethylene glycol (DEG), triethylene glycol, tetraethylene glycol), polypropylene glycols (e.g., dipropylene glycol, tripropylene glycol, tetrapropylene glycol), polymeric glycols (e.g., PEG 200, PEG 300, PEG 400, PPG 400), and thiodiglycol.
Preferably, the organic solvent comprises 1,2 diols of C5-C7, namely, 1,2-pentanediol, 1,2-hexanediol, and 1,2-heptanediol; and most preferably, 1,5-pentanediol is employed in the practice of the invention.
Surfactant
The inks of the present invention optionally comprise 0 to about 10 wt % surfactant. More preferably, the inks comprise from about 0.5 to about 5 wt % surfactant.
In the practice of the invention, one or more surfactants may optionally be used. Non-ionic surfactants, such as secondary alcohol ethoxylates (e.g., Tergitol series available from Union Carbide Co.), non-ionic fluoro surfactants (such as FC170C available from 3M), non-ionic fatty acid ethoxylate surfactants (e.g., Alkamul PSMO-20 available from Rhone-Poulenc), and fatty amide ethoxylate surfactants (e.g., Aldamide L203 available from Rhone-Poulenc) are preferred, with secondary alcohol ethoxylates being the most preferred. In the practice of the invention, the secondary alcohol ethoxylates serve to prevent color to color bleed by increasing the penetration of the inks into the print medium. Secondary alcohol ethoxylates are nonionic surfactants and are commercially available, for example, from Union Carbide Co. (Houston, Tex.) as the Tergitol series. Tergitol 15-S-5 is the preferred surfactant.
The secondary alcohol ethoxylates contain (a) an aliphatic chain having a prescribed number of carbon atoms in the chain, and (b) a prescribed number of ethoxylated units. These ethoxylates are commercially available as mixtures of ethoxylates, and so are described in terms of the predominance of a given compound. Secondary alcohol ethoxylates suitably employed in the practice of the invention predominantly have from about 12 to about 18 carbon atoms in the aliphatic chain, while the number of ethoxylated units is predominantly in the range of from about 4 to about 8 units. Thus, xe2x80x9cTergitol 15-S-5xe2x80x9d represents a secondary alcohol ethoxylate surfactant predominantly having about 15 carbons in its aliphatic chain and about 5 ethoxylated units. Tergitol 15-S-5 is the most preferred surfactant.
Buffer
The inks of the present invention optionally comprise 0 to about 1.5 wt % buffer. More preferably, the inks comprise from about 0.0 to about 0.5 wt % buffer, with a concentration from about 0.0 to about 0.3 wt % being the most preferred. Buffers employed in the practice of the invention to modulate pH can be organic-based. Examples of preferably-employed buffers include Trizma Base, available from companies such as Aldrich Chemical (Milwaukee, Wis.), 4-morpholinepropanesulfonic acid (MES), and 4-morpholinepropanesulfonic acid (MOPS). Buffers employed should provide a pH ranging from about 3 to about 9 in the practice of the invention, preferably about 3 to about 5 and most preferably from about 3.7 to 4.2.
Metal Chelator
The inks of the present invention optionally comprise 0 to about 1.5 wt % metal chelator. More preferably, the inks comprise from about 0.1 to about 0.5 wt % metal chelator, with a concentration from about 0.1 to about 0.3 wt % being the most preferred.
Metal chelators employed in the practice of the invention are used to bind transition metal cations that may be present in the ink. Examples of preferably-employed metal chelators include: Ethylenediaminetetraacetic acid (EDTA), Diethylenetriaminepentaacetic acid (DTPA), trans-1,2-diaminocyclohexanetetraacetic acid (CDTA), (ethylenedioxy) diethylenedinitrilotetraacetic acid (EGTA), or other chelators that can bind transition metal actions. More preferably, EDTA, and DTPA; and most preferably, EDTA in its disodium dihydrate salt form is employed in the practice of the invention.
Biocide
The inks of the present invention optionally comprise 0 to about 5 wt % biocide. More preferably, the inks comprise from about 0 to about 2 wt % biocide, with a concentration from about 0.0 to about 0.5 wt % being the most preferred. Any of the biocides commonly employed in ink-jet inks may be employed in the practice of the invention, such as Nuosept 95, available from Huls America (Piscataway, N.J.); Proxel GXL, available from Zeneca (Wilmington, Del.); and glutaraldehyde, available from Union Carbide Company (Bound Brook, N.J.) under the trade designation Ucarcide 250.